The present invention relates to novel aluminosiloxane compounds represented by the following formulae (1) and (2), processes for preparing same and use thereof. Particularly, the compounds of formulae (1) and (2) according to the present invention have the characteristics to be prepared from waste silicone compounds and to be advantageously used as siloxylating agent for various organic and inorganic materials, specifically for materials containing hydroxy group. 
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
n denotes a number of 6 to 90, and
M represents alkali metal.
Currently used siloxylating agents include silane or siloxane compounds containing reactive hydroxy group(xe2x80x94OH), alkoxy group(xe2x80x94OR), carboxyl group (xe2x80x94OCOR), amine group(xe2x80x94NHR, xe2x80x94NR2), epoxy group 
hydrogen(xe2x80x94H), etc at terminal sites of the molecules, and modified silyl compounds wherein silyl groups are bound to the intramolecular side chains.
The novel aluminosiloxane compounds provided by the present invention belong to hetero metallic siloxane series(xe2x89xa1Sixe2x80x94Oxe2x80x94Mxe2x80x94Oxe2x80x94Sixe2x89xa1) wherein a metal atom is placed between two siloxane groups. The aluminosiloxane compounds according to the present invention not only can replace the existing siloxylating, agent, but also exhibit more strong siliconic characteristics through the formation of a long chain wherein at least six(6) dialkyl(or phenyl)siloxyl units 
are linked with each other. Particularly, the present compounds are expected to have a highly improved properties in reactivity for siloxylation, etc.
Many researches have been made on aluminosiloxanes. For example, aluminosilsesquioxane prepared from isopropoxyaluminum[(i-PrO)2Al] and trialkoxysilane is disclosed in J. Am. Chem. Soc. 1989, 111, 7288-7289 and Inorg Chem. 1999, 38, 210-211. This aluminosilsesquioxane compound is identical with the compounds of the present invention in that Al atom has a AlO4 configuration, but different therefrom in that Si atom has a RSiO3 configuration. Further, a method for endowing aluminum metal surface with anti-corrosion property and gloss by treating the metal surface with ethoxysilane vapour to form xe2x95x90Alxe2x80x94Oxe2x80x94Sixe2x89xa1 bond on the metal surface(see: Journal of the Electrochemical Society V.143, N.1, 1996); a method for forming xe2x95x90Alxe2x80x94Oxe2x80x94Sixe2x89xa1 structure on aluminum metal surface by treating the metal surface with alkoxysilane through a sol-gel method(see: Colloids and Surfaces A: Physicochem. Eng. Aspects 139, 299-310, 1998); a method for synthesizing phosphine ruthernium(Rh) complex by reacting isopropoxyaluminum with alkoxysilane through a sol-gel method(see: Inorg. Chem. 1997, 36, 862-866 and Chem. Mater. 1998, 10, 217-225); and a method for preparing mullite from aluminum and silicone oxide via aluminosiloxane(see: Chem. Mater, 1996, 8, 2056-2060) are disclosed. However, any of the intermediates or final products disclosed in these prior arts does not have a similar structure or property to the novel aluminosiloxane compound provided by the present invention.
Under the technical background as explained above, the present inventors have studied to develop an effective method for decomposition and recovery of siloxane bond-containing compound such as silicone rubber, silicone oil, etc., which ultimately results in decrease of pollution caused by waste silicone compounds and promotion of silicone chemical industry without any concern about waste. As a result, we filed an application for a novel process for decomposing siloxane bond-containing compound characterized in that secondary and/or tertiary aliphatic alcohols are used as a decomposition facilitator, and if desired, the decomposition product is further sonicated and treated with a terminator. The application has now been granted a patent(see, Korean Patent No 190,752, and U.S. Pat. No. 5,892,087). Specifically, the siloxane bond has the advantage of excellent weatherability whereby it is not aged nor decomposed But, such an advantage rather causes the impossibility of natural decomposition after waste of the siloxane bond-containing compounds, which makes them serious pollutional materials. Therefore, the development of said decomposition or recovery process is considered to have a great importance in the aspect of environmental protection.
The present inventors proceeded with our studies to develop a compound which can be effectively utilized as a siloxylating agent by using a siloxane alkali metal salt represented by the following formula (3), which is obtained through the aforementioned decomposition process, as the starting material. Accordingly, the present inventors have synthesized the compounds of formulae (1) and (2) as above and identified structures and uses thereof, and then completed the present invention: 
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
Rxe2x80x2 represents hydrogen or C1-C6-alkyl,
M represents alkali metal, and
m denotes a number of 3 to 6.
The present invention will be more specifically explained hereinafter.
One object of the present invention is to provide aluminosiloxane compounds of the following formula (1) or (2): 
in which
R is identical with or different from each other, and represents C1-C6-alkyl or phenyl,
n denotes a number of 6 to 90, and
M represents alkali metal.
As can be seen from the above formulae (1) and (2), silicon atoms in the aluminosiloxane compound of the present invention are identified through 29Si-NMR to have the configuration of dialkyl(or phenyl)siloxyl unit 
wherein two(2) oxygen atoms and two(2) alkyl(or phenyl) groups are attached to the silicon atom, and aluminum atoms are identified through 27Al-NMR to have the configuration coordinated with four(4) oxygen atoms.
The present compounds characterized by such an unique structure have different molecular weights depending on R, M and n. Further, with the content of M, the compound of formula (1) seems to be associated to form the compound of formula (2). That is, according to G.P.C. molecular weight measurement, the compound of formula (2) having an average molecular weight of 2000 wherein R is methyl, n is 6, and M is natrium(Sample 1 of the following Table 1) may be converted to the compound of formula (1) having an average molecular weight of 1000(Sample 2 of the following Table 1) by the treatment with ammonium chloride(purification=removal of natrium) during which the content of natrium is significantly decreased(1.51%xe2x86x920.55%). Elementary analysis results and n values calculated therefrom for some typical compounds according to the present invention are represented in the following Table 1.
As can be seen from the elementary analysis results of the above Table 1, it has been found that aluminum content is 0.52% and average molecular weight is 5,462(see FIG. 3) in the case of Sample 3(object compound of Example 5) and aluminum content is 0.3% and average molecular weight is 10,948 in the case of Sample 4(object compound of Example 6). If calculated from the elementary analysis results, the n value of Sample 3 is 35 and that of Sample 4 is 65, respectively. Samples 3 and 4 are prepared using different amount of powdered aluminum metal from each other(see Examples 5 and 6). Therefore, it is realized that if the amount of aluminum(starting material) is controlled in the process for preparing the aluminosiloxane compound of the present invention, the n value may be optionally controlled. Upon conducting elementary analyses on the compounds having various molecular weights including the analyses of Table 1, it is identified that 12 to 180 silicon atoms are present for each aluminum atom in the aluminosiloxane compounds of formulae (1) and (2) according to the present invention.
Generally, physico-chemical properties of the aluminosiloxane compound vary depending on the n value. For example, flexibility increases as the n value increases, but if the n value comes close to 90, the compound having such a high n value almost has the state of liquid, which makes the handling thereof difficult(for that reason, the n value is restricted to 90 or less in the present invention). Further, since there is a case requiring high silicone-based properties or a case requiring low silicone-based properties depending on the purpose, it is desirable to prepare an aluminosiloxane compound having a specific n value appropriate for the purpose thereof by considering the correlation between the n value and physico-chemical property.
The aluminosiloxane compounds according to the present invention are soluble in nonpolar organic solvents such as n-hexane, benzene, toluene, tetrahydrofuran, etc. They are stable compounds having, a specific density varying from 0.94 to 0.98, and also stable under atmosphere in the form of gel solid. But, they are not stable in the presence of electron acceptor(H=proton) to be easily dissociated as depicted in the following Reaction Scheme 1. 
Therefore, according to the characteristics as described above, it is considered that condensation reaction may be actively carried out between organic or inorganic substance having hydroxy group or epoxy group at terminals, such as for example, thermosetting resin, cellulose, sucrose, epoxy, and the like and the product obtained from Reaction Scheme 1 optionally in the presence of an acid catalyst The condensation reaction is described in Reaction Scheme 2 below. 
In the above Reaction Scheme 2, if the compound containing hydroxy group is a hydrocarbon compound and the resulting product has a structure of xe2x89xa1Sixe2x80x94Oxe2x80x94Cxe2x89xa1, this linkage is unstable under atmosphere and thus, may have the problem to be readily dissociated again. However, inside the network structure of thermosetting resins such as phenol, melamine, urea, epoxy resins, or inside the macromolecules such as cellulose, the siloxane group may form a hybrid structure or stable interpenetrating polymer networks(IPN) which is caused by rearrangement from xe2x89xa1Sixe2x80x94Oxe2x80x94Cxe2x89xa1 to siloxane(xe2x89xa1Sixe2x80x94Oxe2x80x94Sixe2x89xa1) bond. Therefore, it is anticipated that compounds of the present invention may be used as a useful siloxylating agent for those thermosetting resins or macromolecules having a network structure. That is, if the aluminosiloxane compound according to the present invention is applied in the final step of preparing those thermosetting resins or macromolecules such as cellulose, the final product may be improved in its physico-chemical properties such as gloss, flexibility, water repellence, heat stability, weatherability, etc.
Further, the aluminosiloxane compound of the present invention may be effectively used as a siloxylating agent for the surface of glass products made from metallic silicate. This is because the aluminosiloxane compound is decomposed in the presence of an acid to have reactive functional groups such as 
or 
(wherein R is hydrogen or alkyl) at terminals, and the functional groups are readily reacted with HOxe2x80x94Sixe2x89xa1 group on the surface of glass products to form a strong bond.
Therefore, compound of formula (1) or (2) according to the present invention can be used as a superior siloxylating agent for the surface of thermosetting resins, cellulose, epoxy, metallic silicates, pigments made from various metallic oxides and other microorganisms to silanes having the existing functional groups. Therefore, another object of the present invention is to provide such a use. Particularly, when the compound of the present invention is used as a siloxylating agent, each siloxylation is carried out with minimum 6 to maximum 90 dialkyl(or phenyl)siloxyl units 
Therefore, materials siloxyated therewith show well established siloxane-based characteristics.
Siloxylation with the aluminosiloxane compounds of the present invention can be carried out in a conventional manner. However, in case of the materials which form a IPN structure during the siloxylation procedure, such as for example epoxy resins, the aluminosiloxane compound according to the present invention is mixed with the epoxy resin in the ratio of 9:1 to 5:5, preferably 8:2 to 7:3 by weight to form a copolymer first and then this copolymer is properly mixed with the epoxy resin to carry out siloxylation procedure.
The desirable amount when used as a siloxylating agent may be easily determined by the person skilled in the art considering the material to be siloxylated, specific structure of the siloxylating agent and the purpose of siloxylation. Generally, the siloxylating agent is used in an amount of 2 to 10% by weight, preferably 2 to 6% by weight with respect to the material to be siloxylated. When the siloxylating agent is not used in the amount as defined above, it may cause some deterioration of physico-chemical properties of the target material or insufficient siloxylation which does not come up to the expectation.
The aluminosiloxane compound of formula (2) according to the present invention can be prepared by a process characterized in that
(i) the siloxane alkali metal salt of formula (3) is reacted with aluminum compound and secondary or tertiary alcohol to produce a hydrophilic compound represented by the following formula (4): 
in which
R and Rxe2x80x2 are defined as previously described,
Rxe2x80x3 is identical with or different from each other, and represents Rxe2x80x2 or M, but with at least one of Rxe2x80x3 being different from Rxe2x80x2, and
mxe2x80x2 is identical with or different from each other, and denotes numbers which make the n value in the resulting compound of formula (2) 6 to 90,
(ii) the compound of formula (4) is reacted with hydrohalic acid under a condition of pH 7 to 8 to produce an oil-miscible compound represented by the following formula (5): 
in which
R and Rxe2x80x2 are defined as previously described, and
mxe2x80x3 is identical with or different from each other, and denotes numbers which make the n value in the resulting compound of formula (2) 6 to 90, and
(iii) the compound of formula (5) is heated at temperatures ranging from 80 to 220xc2x0 C.
During the procedure of preparing the compound of formula (2) via compounds 4 and 5, the number of siloxyl units(i.e., mxe2x80x2 or mxe2x80x3) is increased due to the successive condensation reactions and the degree of increase may be determined by the amount of aluminum compound introduced. That is, the small amount of aluminum compound leads to a lot of condensation reactions which make the number of siloxyl units and ultimately the n value increase and vice versa. Therefore, it is another object of the present invention to provide such a preparation process.
The above process for preparing the compound of formula (2) may be summarized as the following Reaction Scheme 3. 
In Step (i) of the above process for preparing compound(2), the siloxane alkali metal salt of formula (3) includes any alkali metal salts, for example salts with lithium, sodium, potassium, etc., however sodium salt is preferable in view of the easiness of reaction and economy. As the reactant aluminum compound, aluminum metal, or hydroxide, oxide, alkali metal salt, halide, inorganic acid(sulfate, nitrate, etc.) salt of aluminum, such as for example, Al, Al(OH)3, Al2O3, AlCl3, AlO2Na may be used. Among them, aluminum metal is most preferable in view of the easiness of reaction and economy. Aluminum compound is used in an amount to make the Si/Al mole ratio in the resulting compound of formula (2) or (1) 12 to 180. As stated above, the n value of the final compound of formula (2) or (1) varies according to the amount of aluminum compound used. Reaction is carried out under room temperature or warming. Reaction temperature may be different according to the kind of aluminum compound used. For example, room temperature is preferred when aluminum metal is used, and some warming is required when aluminum chloride is used. Alcohol compound participated in the reaction should be secondary or tertiary alcohols, and isopropyl alcohol or t-butyl alcohol is particularly preferable. The resulting compound of formula (4) thus obtained by the reaction as explained above is hydrophilic.
In Step (ii), the compound of formula (4) is reacted with hydrohalic acid under a condition of pH 7 to 8 to produce the compound of formula (5). As the hydrohalic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, preferably hydrochloric acid can be used. The reaction is carried out by adding a basic compound to the reaction solution containing the compound of formula (4) first to make the solution alkaline (pH range of about 8 to about 10) and then by adding the reactant hydrohalic acid thereto in an amount required to control the pH value of the reaction solution to 7 to 8. As the basic compound, ammonia compound, particularly ammonia gas or ammonia water is used in an amount to make the reaction solution alkaline. When an alkali metal-containing compound is used as the basic compound instead of the ammonia compound, additional purification steps may be required depending on the purpose of the resulting aluminosiloxane compound and thus, not desirable. Through such a neutralization procedure, the oil-miscible and multi-functional compound of formula (5) is obtained.
Finally in Step (iii), the compound of formula (5) is heated under normal pressure and temperatures of 80 to 220xc2x0 C., preferably 100 to 160xc2x0 C. to produce the desired compound of formula (2) which does not have any terminal functional groups.
On the other hand, the aluminosiloxane compound of formula (1) according to the present invention, which is deficient in M, can be prepared by a process characterized in that
(a) the compound of formula (2) is reacted with a compound represented by the followings formula (6)
NRxe2x80x23HXxe2x80x83xe2x80x83(6)
xe2x80x83in which
Rxe2x80x2 is defined as previously described, and
X represents halogen, in a non-polar solvent, or
(b) a compound represented by the following formula (7): 
in which
R, Rxe2x80x2 and m are defined as previously described, and
Rxe2x80x3xe2x80x2 represents C1-C6-alkyl, is reacted with aluminum compound and secondary or tertiary alcohol, and then alcohol is removed therefrom.
In process variant (a) above, it is most preferable to use ammonium chloride(i.e., Rxe2x80x2 is hydrogen and X is chlorine) among the compound of formula (6) which is used as a reactant. Reaction is carried out for 3 to 5 hours under normal temperature and pressure because silicone oil may be separated from the resulting aluminosiloxane compound when the reaction mixture is heated. Since the compound of formula (6) is used for the purpose of removing M which is present in the compound of formula (2), it is preferable to use the compound of formula (6) in an equimolar amount to the compound of formula (2). As the non-polar solvent, one or more selected from n-hexane, toluene, tetrahydrofuran, bezene and xylene can be mentioned.
In process variant (b) above, if the compound of formula (7) is used as the starting material, the desired compound of formula (1) is directly produced without any need to use the hydrohalic acid. Here, the same aluminum compound and secondary or tertiary alcohol compound as explained in the process for preparing the compound of formula (2) may be used. When the compound of formula (7) is reacted with aluminum compound and alcohol, the reaction is preferably carried out at temperatures ranging from 60 to 80xc2x0 C.
Although only aluminum compound is exemplified in the above processes according to the present invention, various forms of zinc(Zn) or tin(Sn) compound, such as for example, hydroxides, oxides, alkali metal salts, halides, acid addition salts(sulfate, nitrate, etc.) thereof besides the aluminum compound may be also reacted with siloxane alkali metal salt of formula (3) in the same manner as the aluminum compound to produce siloxane compounds containing various metals.
The present invention will be more specifically explained in the following examples. However, it should be understood that the following examples are intended to illustrate the present invention but not in any manner to limit the scope of the present invention.